Process for preparing compositions useful as intermediates for preparing lubricating oil and fuel additives and derivatives thereof

ABSTRACT

A process for reacting certain carboxylic reactants with olefinic compounds then reacting the intermediate prepared thereby with ammonia, a hydrazine or an amine, and/or a reactive metal or reactive metal compound, products prepared thereby and, additive concentrates and lubricating oil and fuel compositions.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of application Ser. No.08/694,139 filed Aug. 8, 1996, now U.S. Pat. No. 5,779,742, which ishereby incorporated herein by reference.

FIELD OF THE INVENTION

This invention relates to a process for preparing compositions which areuseful as intermediates for the preparation of low chlorine containingadditives for lubricating oils and normally liquid fuels, compoundsprepared by the process, and derivatives thereof.

BACKGROUND OF THE INVENTION

Numerous types of additives are used to improve lubricating oil and fuelcompositions. Such additives include, but are certainly not limited todispersants and detergents of the ashless and ash-containing variety,oxidation inhibitors, anti-wear additives, friction modifiers, and thelike. Such materials are well known in the art and are described in manypublications, for example, Smalheer, et al, "Lubricant Additives",Lezius-Hiles Co., Cleveland, Ohio, U.S.A. (1967); M. W. Ranney, Ed.,"Lubricant Additives", Noyes Data Corp., Park Ridge, N.J., U.S.A.(1973); M. J. Satriana, Ed., "Synthetic Oils and Lubricant Additives,Advances since 1977", Noyes Data Corp., Park Ridge N.J., U.S.A. (1982),W. C. Gergel, "Lubricant Additive Chemistry", Publication 694-320-65R1of the Lubrizol Corp., Wickliffe, Ohio, U.S.A. (1994); and W. C. Gergelet al, "Lubrication Theory and Practice" Publication 794-320-59R3 of theLubrizol Corp., Wickliffe, Ohio, U.S.A. (1994); and in numerous UnitedStates patents, for example Chamberlin, III, U.S. Pat. No. 4,326,972,Schroeck et al, U.S. Pat. No. 4,904,401, Blystone et al., U.S. Pat. No.5,356,546 and Ripple et al, U.S. Pat. No. 4,981,602. Many such additivesare frequently derived from carboxylic reactants, for example, acids,esters, anhydrides, lactones, and others. Specific examples of commonlyused carboxylic compounds used as intermediates for preparinglubricating oil additives include alkyl- and alkenyl substitutedsuccinic acids and anhydrides, polyolefin substituted carboxylic acids,aromatic acids, such as salicylic acids, and others. Illustrativecarboxylic compounds are described in Meinhardt, et al, U.S. Pat. No.4,234,435; Norman et al, U.S. Pat. No. 3,172,872; LeSuer et al, U.S.Pat. No. 3,454,607, and Rense, U.S. Pat. No. 3,215,707.

Many carboxylic intermediates used in the preparation of lubricating oiladditives contain chlorine. While the amount of chlorine present isoften only a very small amount of the total weight of the intermediate,the chlorine frequently is carried over into the carboxylic derivativewhich is desired as an additive. For a variety of reasons, includingenvironmental reasons, government regulation, and commercial reasons theindustry has been making efforts to reduce or to eliminate chlorine fromadditives designed for use as lubricant or fuel additives. The matter ofchlorine content in additives is discussed in numerous patents includingU.S. Pat. Nos. 5,356,552; 5,370,805; 5,445,657 and 5,454,964.

Accordingly, it is desirable to provide low chlorine or chlorine freeadditives and intermediates useful for preparing them for use inlubricants and fuels.

The present invention provides an improved process and products preparedby the improved process and derivatives which meet these requirements.

B. B. Snider and J. W. van Straten, J. Org. Chem., 44, 3567-3571 (1979)describe certain products prepared by the reaction of methyl glyoxylatewith several butenes and cyclohexenes. K. Mikami and M. Shimizu, Chem.Rev., 92, 1021-1050 (1992) describe carbonyl-ene reactions, includingglyoxylate-ene reactions. D. Savostianov (communicated by P. Pascal),C.R. Acad. Sc. Paris, 263, (605-7) (1966) relates to preparation of someα-hydroxylactones via the action of glyoxylic acid on olefins. M.Kerfanto et. al., C.R. Acad. Sc. Paris, 264, (232-5) (1967) relates tocondensation reactions of α-α-di-(N-morpholino)-acetic acid andglyoxylic acid with olefins. B. B. Jarvis et al, Synthesis, 1079-82(1990) relates to reactions of oxocarboxylic acids with olefins underacidic conditions to give α-hydroxy butyrolactones.

Fuels containing additives to improve the performance thereof aredescribed in numerous patents including the following United Statespatents:

    ______________________________________                                               4,071,327                                                                            5,336,278                                                         4,379,065 5,356,546                                                           4,400,178 5,458,793                                                           4,564,460                                                                   ______________________________________                                    

SUMMARY OF THE INVENTION

The present invention provides a process comprising reacting, optionallyin the presence of an acidic catalyst selected from the group consistingof organic sulfonic acids, heteropolyacids, Lewis acids, and mineralacids,

(A) at least one olefinic compound containing at least one group of theformula ##STR1## (B) at least one carboxylic reactant selected from thegroup consisting of compounds of the formula ##STR2## wherein each ofR³, R⁵ and one R⁹ is independently H or a hydrocarbyl group and theother R⁹ is a hydrocarbyl group, R⁴ is a divalent hydrocarbylene group,and n is 0 or 1, in amounts ranging from 0.6 moles (B) per mole of (A)to 3 moles (B) per equivalent of (A).

Products prepared by the process and derivatives thereof, e.g., withamines, basic metal compounds, alcohols, etc., are also contemplated.

Also provided are additive concentrates for preparing lubricating oiland fuel compositions, lubricating oil compositions and fuelcompositions.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

As used herein, the terms "hydrocarbon", "hydrocarbyl" or "hydrocarbonbased" mean that the group being described has predominantly hydrocarboncharacter within the context of this invention. These include groupsthat are purely hydrocarbon in nature, that is, they contain only carbonand hydrogen. They may also include groups containing non-hydrocarbonatom containing substituents or atoms which do not alter thepredominantly hydrocarbon character of the group. Such substituents mayinclude halo-, alkoxy-, nitro-, etc. These groups also may containhetero atoms. Suitable hetero atoms will be apparent to those skilled inthe art and include, for example, sulfur, nitrogen and oxygen.Therefore, while remaining predominantly hydrocarbon in character withinthe context of this invention, these groups may contain atoms other thancarbon present in a chain or ring otherwise composed of carbon atoms.

In general, no more than about three non-hydrocarbon substituents orhetero atoms, and preferably no more than one, will be present for every10 carbon atoms in the hydrocarbon, hydrocarbyl or hydrocarbon basedgroups. Most preferably, the groups are purely hydrocarbon in nature,that is they are essentially free of atoms other than carbon andhydrogen.

Throughout the specification and claims the expression soluble ordispersible is used. By soluble or dispersible is meant that an amountneeded to provide the desired level of activity or performance can beincorporated by being dissolved, dispersed or suspended in an oil oflubricating viscosity or in a normally liquid fuel. Usually, this meansthat at least about 0.001% by weight of the material can be incorporatedin a lubricating oil or normally liquid fuel. For a further discussionof the terms oil soluble and dispersible, particularly "stablydispersible", see U.S. Pat. No. 4,320,019 which is expresslyincorporated herein by reference for relevant teachings in this regard.

As noted hereinabove, provided by this invention is a process forpreparing low chlorine or chlorine free compositions useful as lowchlorine or chlorine free additives and intermediates for preparing suchadditives for lubricating oil and fuel compositions.

The Process

In one embodiment, the present invention relates to a process comprisingreacting, optionally in the presence of an acidic catalyst selected fromthe group consisting of organic sulfonic acids, heteropolyacids, Lewisacids, and mineral acids,

(A) at least one olefinic compound containing at least one group of theformula ##STR3## and (B) at least one carboxylic reactant selected fromthe group consisting of compounds of the formula ##STR4## wherein eachof R³, R⁵ and one R⁹ is independently H or a hydrocarbyl group and theother R⁹ is a hydrocarbyl group, R⁴ is a divalent hydrocarbylene group,and n is 0 or 1, in amounts ranging from 0.6 moles (B) per mole of (A)to 3 moles (B) per equivalent of (A).

Reactants (A) and (B) may be present at the outset of the reaction.Under these conditions, all of (A) and (B) may be present at the sametime; however, it has been found that improvements in yield and purityof the product arising from the reaction of (A) and (B) are oftenattained when the carboxylic reactant (B) is added to the olefiniccompound (A) either portionwise or continuously over an extended periodof time, usually up to about 10 hours, more often from 1 hour up toabout 6 hours, frequently from about 2 to about 4 hours.

Optionally the process may be conducted in the presence of a solvent.Well known solvents include aromatic and aliphatic solvents, oil, etc.When a solvent is used, the mode of combining reactants does not appearto have any effect.

The process may be conducted in the presence of an azeotroping solvent.Well known azeotroping solvents include toluene, xylene, cyclohexane,etc. Cyclohexane is preferred.

Reactant (B) can be mixed with the olefinic compound all at once as in abatch reaction or can be added dropwise or metered into a reactor over aperiod of time. Compared to glyoxylic acid and homologs thereof theacetals, ketals, hemiacetals, and hemiketals, and especially the esters,are more miscible with the olefinic compound owing to the lower polaritythereof compared to a carboxylic acid such as glyoxylic acid.Furthermore, the absence of water in the carboxylic reactant (B) makesmixing with the olefinic compound easier than mixing of glyoxylic andthe olefinic compound. However, it is still important to insure goodmixing especially in large scale synthesis.

The Catalyst

The process of this invention is optionally conducted in the presence ofan acidic catalyst. Acid catalysts, such as organic sulfonic acids, forexample, paratoluene sulfonic acid, methane sulfonic acid and sulfonatedpolymers such as those marketed under the tradename Amberlyst® (Rohm &Haas), heteropolyacids, the complex acids of heavy metals (e.g., Mo, W,Sn, V, Zr, etc.) with phosphoric acids (e.g., phosphomolybdic acid), andmineral acids, for example, H₂ SO₄ and phosphoric acid, are useful. Theamount of catalyst used is generally small, ranging from about 0.01 mole% to about 10 mole %, more often from about 0.1 mole % to about 2 mole%, based on moles of olefinic reactant.

(A) The Olefinic Compound

The olefinic compound employed as a reactant in the process of thisinvention contains at least one group of the formula ##STR5## and hasthe general formula

    (R.sup.1)(R.sup.2)C═C(R.sup.6)(CH(R.sup.7)(R.sup.8))   (III)

wherein each of R¹ and R² is, independently, hydrogen or a hydrocarbonbased group. Each of R⁶, R⁷ and R⁸ is, independently, hydrogen or ahydrocarbon based group; preferably at least one is a hydrocarbon basedgroup containing at least 7 carbon atoms. These olefinic compounds arediverse in nature.

Virtually any compound containing an olefinic bond may be used providedit meets the general requirements set forth hereinabove for (III) anddoes not contain any functional groups (e.g., primary or secondaryamines) that would interfere with the carboxylic reactant (B). Usefulolefinic compounds may be terminal olefins, i.e., olefins having a H₂C═C group, or internal olefins. Useful olefinic compounds may have morethan one olefinic bond, i.e., they may be dienes, trienes, etc. Mostoften they are mono-olefinic. Examples include linear ∝-olefins, cis- ortrans- disubstituted olefins, trisubstituted olefins andtetrasubstituted olefins.

When (A) is a monoolefinic, one mole of (A) contains one equivalent ofC═C; when (A) is diolefinic, one mole of (A) contains 2 equivalents ofC═C bonds; when (A) is triolefinic, one mole of (A) contains 3equivalents of C═C bonds, and so forth.

Aromatic double bonds are not considered to be olefinic double bondswithin the context of this invention.

As used herein, the expression "polyolefin" defines a polymer derivedfrom olefins. The expression "polyolefinic" refers to a compoundcontaining more than one C═C bond.

Among useful compounds are those that are purely hydrocarbon, i.e.,those substantially free of non-hydrocarbon groups or atoms, or they maycontain one or more non-hydrocarbon groups or atoms as discussed ingreater detail herein.

In one embodiment, the olefinic compounds are substantially hydrocarbon,that is, each R group in (III) is H or contains essentially carbon andhydrogen. In one aspect within this embodiment, each of R¹, R², R⁷ andR⁸ is hydrogen and R⁶ is a hydrocarbyl group containing from 7 to about5,000 carbon atoms, more often from about 30 up to about 200 carbonatoms, preferably from about 50 up to about 100 carbon atoms. In anotheraspect of this embodiment, each of R¹ and R² is hydrogen, R⁶ is H or alower alkyl group, especially methyl, and the group (CH(R⁷)(R⁸)) is ahydrocarbyl group containing from 7 to about 5,000 carbon atoms, moretypically from about 30 up to about 200 carbon atom, preferably from 50up to about 100 carbon atoms.

As used here, and throughout the specification and claims, theexpression "lower" with "alkyl", "alkenyl", etc. means groups having 7or fewer carbon atoms, for example, methyl, ethyl and all isomers ofpropyl, butyl, pentyl, hexyl and heptyl, ethylene, butylene, etc.

In another embodiment, one or more of the R groups present in (III) isan organic radical which is not purely hydrocarbon. Such groups maycontain or may be groups such as carboxylic acid, ester, amide, salt,including ammonium, amine and metal salts, cyano, hydroxy, thiol,tertiary amino, nitro, alkali metal mercapto and the like. Illustrativeof olefinic compounds (III) containing such groups are methyl oleate,oleic acid, 2-dodecenedioic acid, octene diol, linoleic acid and estersthereof, and the like.

Preferably, the hydrocarbyl groups are aliphatic groups. In onepreferred embodiment, when an R group is an aliphatic group containing atotal of from about 30 to about 100 carbon atoms, the olefinic compoundis derived from homopolymerized and interpolymerized C₂₋₁₈ mono- anddi-olefins, preferably 1-olefins. In a preferred embodiment, the olefinscontain from 2 to about 5 carbon atoms, preferably 3 or 4 carbon atoms.Examples of such olefins are ethylene, propylene, butene-1, isobutylene,butadiene, isoprene, 1-hexene, 1-octene, etc. R groups can, however, bederived from other sources, such as monomeric high molecular weightalkenes (e.g. 1-tetracontene), aliphatic petroleum fractions,particularly paraffin waxes and cracked analogs thereof, white oils,synthetic alkenes such as those produced by the Ziegler-Natta process(e.g., poly-(ethylene) greases) and other sources known to those skilledin the art. Any unsaturation in the R groups may be reduced byhydrogenation according to procedures known in the art, provided atleast one olefinic group remains as described for (III).

In one preferred embodiment, at least one R is derived from polybutene,that is, polymers of C₄ olefins, including 1-butene, 2-butene andisobutylene. Those derived from isobutylene, i.e., polyisobutylenes, areespecially preferred. In another preferred embodiment, R is derived frompolypropylene. In another preferred embodiment, R is derived fromethylene-alpha olefin polymers, including ethylene-α-olefin-dienepolymers, especially those wherein the diene is a non-conjugated diene.Representative of such polymers are the ethylene-propylene copolymersand ethylene-propylene-diene terpolymers marketed under the Trilene®tradename by the Uniroyal Company. Molecular weights of such polymersmay vary over a wide range, but especially preferred are those havingnumber average molecular weights (M_(n)) ranging from about 300 up to20,000, preferably about 700 to about 10,000, often from about 900 toabout 2,500. In one preferred embodiment, the olefin is anethylene-propylene-diene terpolymer having M_(n) ranging from about 900to about 8,000, often up to about 2,000. Such materials are includedamong the Trilene® polymers marketed by the Uniroyal Company,Middlebury, Conn., U.S.A. Also contemplated are polydiene polymers,those prepared by polymerizing dienes.

Ethylene-alpha olefin copolymers and ethylene-lower olefin-dieneterpolymers are described in numerous patent documents, includingEuropean patent publication EP 279,863, Japanese patent publication87-129,303 and the following United States patents:

    ______________________________________                                               3,598,738                                                                            4,357,250                                                         4,026,809 4,658,078                                                           4,032,700 4,668,834                                                           4,137,185 4,937,299                                                           4,156,061 5,324,800                                                           4,320,019                                                                   ______________________________________                                    

each of which is incorporated herein by reference for relevantdisclosures of these ethylene based polymers

A preferred source of hydrocarbyl groups R are polybutenes obtained bypolymerization of a C₄ refinery stream having a butene content of 35 to75 weight percent and isobutylene content of 15 to 60 weight percent inthe presence of a Lewis acid catalyst such as aluminum trichloride orboron trifluoride. These polybutenes contain predominantly (greater than80% of total repeating units) isobutylene repeating units of theconfiguration ##STR6## These polybutenes are typically monoolefinic,that is they contain but one olefinic bond per molecule.

The olefinic compound may be a polyolefin comprising a mixture ofisomers wherein from about 50 percent to about 65 percent aretri-substituted olefins wherein one substituent contains from 2 to about500 carbon atoms, often from about 30 to about 200 carbon atoms, moreoften from about 50 to about 100 carbon atoms, usually aliphatic carbonatoms, and the other two substituents are lower alkyl.

When the olefin is a tri-substituted olefin, it frequently comprises amixture of cis- and trans- 1-lower alkyl, 1-(aliphatic hydrocarbylcontaining from 30 to about 100 carbon atoms), 2-lower alkyl ethene and1,1-di-lower alkyl, 2-(aliphatic hydrocarbyl containing from 30 to about100 carbon atoms) ethene.

In one embodiment, the monoolefinic groups are predominantly vinylidenegroups, i.e., groups of the formula ##STR7## especially those of theformula ##STR8## although the polybutenes may also comprise otherolefinic configurations.

In one embodiment the polybutene is substantially monoolefinic,comprising at least about 30 mole %, preferably at least about 50 mole %vinylidene groups, more often at least about 70 mole % vinylidenegroups. Such materials and methods for preparing them are described inU.S. Pat. Nos. 5,071,919; 5,137,978; 5,137,980; 5,286,823 and 5,408,018,and in published European patent application EP 646103-A1, each of whichis expressly incorporated herein by reference. They are commerciallyavailable, for example under the tradenames Ultravis (BP Chemicals) andGlissopal (BASF).

In one embodiment, the olefinic compound is a polyolefin comprising amixture of isomers, at least about 50% by weight of the mixturecomprising isomers of the formula

    H.sub.2 C═C(R.sup.6)(CH(R.sup.7)(R.sup.8))

wherein R⁶ is H or lower alkyl, preferably methyl.

As is apparent from the foregoing, olefins of a wide variety of type andof molecular weight are useful for preparing the compositions of thisinvention. Useful olefins are usually substantially hydrocarbon and havenumber average molecular weight ranging from about 100 to about 70,000,more often from about 200 to about 7,000, even more often from about1,300 to about 5,000, frequently from about 400 to about 3,000. Lowerolefins such as those containing from about 7 to about 30 carbon atoms,for example, octenes, octadecenes, mixed olefin, such as C₈₋₂₈ linearolefins, are useful. Linear alpha-olefins containing from 7-100 carbonatoms, preferably from 8-50 carbons and offer from 8 to about 28 carbonatoms are useful.

Specific characterization of olefin reactants (A) used in the processesof this invention can be accomplished by using techniques known to thoseskilled in the art. These techniques include general qualitativeanalysis by infrared and determinations of average molecular weight,e.g., M_(n), number average molecular weight, and M_(w), weight averagemolecular weight, etc. employing vapor phase osmometry (VPO) and gelpermeation chromatography (GPC).

Viscosity average molecular weights (Mv) have widely been used inpolymer chemistry as approximations of weight average molecular weights.The value of Mv is close to that of Mw. The magnitude of the threeaverage molecular weights are:

    Mw>Mv>Mn

Mv is calculated from intrinsic viscosity.

Intrinsic viscosity is a physical constant of a polymer. It is themeasure of the ability of a polymer to increase the viscosity of asolvent when the polymer is dissolved in the solvent. The viscosity ofthe solution is markedly greater than that of the solvent. This is oneof the striking properties which high molecular weight compoundspossess. Intrinsic viscosity is a thickening coefficient of a polymer insolution.

Structural details can be elucidated employing proton and carbon 13(C¹³) nuclear magnetic resonance (NMR) techniques. NMR is useful fordetermining substitution characteristics about olefinic bonds, andprovides some details regarding the nature of the substituents. Morespecific details regarding substituents about the olefinic bonds can beobtained by cleaving the substituents from the olefin by, for example,ozonolysis, then analyzing the cleaved products, also by NMR, GPC, VPO,and by infra-red analysis and other techniques known to the skilledperson.

(B) The Carboxylic Reactant

The carboxylic reactant is at least one member selected from the groupconsisting of compounds of the formula ##STR9## wherein each of R³, andone R⁹ is independently H or a hydrocarbyl group and the other R⁹ is ahydrocarbyl group.

R³ is usually H or an aliphatic group, that is, alkyl or alkenyl,preferably alkyl, more preferably lower alkyl. Especially preferred iswhere R³ is H or methyl, most preferably, H.

R⁴ is a divalent hydrocarbylene group. This group may be aliphatic oraromatic, but is usually aliphatic. Often, R⁴ is an alkylene groupcontaining from 1 to about 3 carbon atoms. The `n` is 0 or 1; that is,in one embodiment R⁴ is present and in another embodiment, R⁴ is absent.More often, R⁴ is absent.

When R⁵ is hydrocarbyl, it is usually an aliphatic group, often a groupcontaining from 1 to about 30 carbon atoms, often from 8 to about 18carbon atoms. In another embodiment, R⁵ is lower alkyl, wherein "loweralkyl" is defined hereinabove. Most often, R⁵ is H or lower alkyl,especially methyl, ethyl, propyl and butyl.

One R⁹ is H or hydrocarbyl, preferably H or alkyl, preferably loweralkyl, especially methyl, ethyl, propyl and butyl. The other R⁹ ispreferably lower alkyl, most preferably methyl, ethyl, propyl or butyl.

Examples of carboxylic reactants (B) are the hemiacetals and hemiketalsof omega-oxoalkanoic acids such as glyoxylic acid and keto alkanoicacids such as pyruvic acid, levulinic acid, ketovaleric acids, andketobutyric acids, and the corresponding acetals and ketals, andnumerous others. The skilled worker, having the disclosure before him,will readily recognize the appropriate compound of formula (V) to employas a reactant to generate a given compound.

In a preferred embodiment, R³ and one R⁹ are hydrogen and the other R⁹and R⁵ are methyl. In this preferred embodiment, the reactant isrepresented by the structure ##STR10## and known as glyoxylic acidmethylester methylhemiacetal. It is marketed by DSM Fine Chemicals.

The process comprising reacting (A) and (B) is conducted at temperaturesranging from ambient up to the lowest decomposition temperature of anyof the reactants, usually from about 60° C. to about 220° C., more oftenfrom about 120° C. to about 180° C., preferably up to about 160° C. Whenthe reaction is conducted in the presence of organic sulfonic acid ormineral acid catalyst, the reaction is usually conducted at temperaturesup to about 160° C. The process employs from about 0.6 moles of reactant(B) per mole of olefinic compound (A), up to 3 moles (B) per equivalentof (A). In one embodiment the process employs from about 0.8 moles (B)per mole of (A) to about 1.2 moles (B) per equivalent of (A), even moreoften from about 0.95 moles (B) per mole of (A) to about 1.05 moles (B)per equivalent of (A). In another embodiment the process employs morethan 1.5 moles, preferably from about 1.6 to about 3 moles of reactant(B) per equivalent of reactant (A), more often from about 1.8 to about2.5 moles of (B) per equivalent of (A) and preferably from about 1.9 toabout 2.1 moles (B) per equivalent of (A). Removal of distillate, eitherfrom reactants or which is generated during reaction, at moderatetemperatures is attainable employing reduced pressure, a solvent thataids in azeotropic distillation, or by purging with an inert gas such asN₂.

The progress of the reaction of (A) and (B) can be followed by observingthe infra-red spectrum. The absorption for --COOH carbonyl of theproducts appears at about 1710 cm⁻¹. The total acid number as measuredusing essentially the procedure in ASTM D-664 (Potentiometric Method) orASTM D-974 (Color Indicator Method) is useful together with theinfrared, keeping in mind that non-acidic products (e.g., polyesterproducts), those derived from non-acidic reactants and condensationproducts such as lactones will not display significant acid numbers.

These ASTM procedures appear in the Annual Book of ASTM Standards,Volume 05.01, ASTM, 1916 Race Street, Philadelphia, Pa., U.S.A.

As noted hereinabove, products obtained by the process of this inventionare provided.

The following examples are intended to illustrate several intermediatecompositions of this invention as well as means for preparing same.Unless indicated otherwise all parts are parts by weight, filtrationsare conducted employing a diatomaceous earth filter aid, and analyticalvalues are by analysis. The abbreviations GPC and VPO refer to gelpermeation chromatography and vapor phase osmometry, respectively, bothprocedures being used to determine molecular weight. The abbreviationTLC-FID refers to thin layer chromatography using a flame ionizationdetector. TLC-FID is used to determine amounts of unreacted olefinicreactant. Saponification numbers are determined using ASTM ProcedureD-94. It is to be understood that these examples are not intended tolimit the scope of the invention.

EXAMPLE 1-A

A reactor is charged with 250 parts of polyisobutylene (GlissopalES3250, BASF) having M_(n) about 1000 and containing about 75 molepercent terminal vinylidene groups, 60 parts glyoxylic acid, methylester, methyl hemiacetal (GMHA) and 1.5 part 70% aqueous methanesulfonic acid. These are heated with mixing, under N₂, to 120° C. andare held at temperature for a total of 6 hours, collecting 11.2 partsdistillate. The temperature is increased 160° C. and held there for 6hours, collecting 4 parts distillate, then for 7 more hours, collecting0.7 parts distillate. The materials are mixed and heated with 50 partswater at 100° C. for 7 hours, collecting 21.2 parts distillate. Thematerials are stripped to 130° C. at 25 mm Hg and filtered. M_(n) (GPC):98.6%=1385.

EXAMPLE 2-A

A reactor is charged with 2088 parts of polyisobutylene (Glissopal 1000)having M_(n) about 1000 and about 90% terminal vinylidine groups, 288parts GMHA, 3 parts 70% aqueous methane sulfonic acid, and 0.1 partssilicone antifoam. The materials are heated with mixing under N₂, to135° C. and are held at temperature for 6 hours, collecting 85 partsdistillate. The materials are heated to 145° C. and filtered. Thefiltrate has saponification number=43.7, and contains 14.4% unreactedpolyisobutylene.

EXAMPLE 3-A

A reactor is charged with 650 parts of the polyisobutylene used inExample 2-A, 78 parts GMHA, 6 parts titanium isopropoxide and 0.1 partsilicone antifoam. The materials are heated, under N₂, to 125° C. andheld at temperature for 6 hours while collecting 32 parts distillate.The materials are filtered at 125° C. The product has saponificationnumber=31.9, and contain 49.9% unreacted polyisobutylene.

EXAMPLE 4-A

A reactor is charged with 350 parts of polyisobutylene (GlissopalES3252) having M_(n) about 2,400 and containing about 70 mole percentterminal vinylidine groups, 21 parts GMHA, 2 parts 70% aqueous methanesulfonic acid, and 0.1 part silicone antifoam. The materials are heated,under N₂, to 120° C. and reacted at 120° C. for 7 hours. The materialsare stripped to 120° C. and 25 mm Hg and filtered. The filtrate hassaponification number=17.9, and unreacted polyisobutylene about 20.3%.

EXAMPLE 5-A

A reactor is charged with 810 parts of the polyisobutylene of Example4-A, 81 parts GMHA, 5 parts methane sulfonic acid and 0.1 part siliconeantifoam. The materials are heated to 125° C., under N₂, and heated for6 hours at 125° C. collecting distillate in a Dean-Stark trap. Thematerials are filtered at 140° C. The filtrate has saponificationnumber=49.3 and 7.4% unreacted polyisobutylene.

EXAMPLE 6-A

A reactor is charged with 350 parts polyisobutylene (Ultravis 10, BPChemicals) having M_(n) about 1,000 and containing about 80 mole percentterminal vinylidine groups, 50.4 parts GMHA, and 4 parts 70% aqueousmethane sulfonic acid. The materials are heated, under N₂, to 120° C.and are then reacted at 120° C. for a total of 10 hours while collectingdistillate. The materials are stripped to 120° C. and 5 mm Hg andfiltered. The filtrate contains 12.7% unreacted polyisobutylene and hassaponification number=44.

EXAMPLE 7-A

A reactor is charged with 5275 parts of the polyisobutylene of Example6-A, 760 parts GMHA, 20 parts methane sulfonic acid, and 0.1 partsilicone antifoam. The materials are heated, under N₂, to 135° C. andare held at temperature for 6 hours while collecting 210.5 partsdistillate. The materials are then stripped to 135° C. at 10 mm Hg for 3hours then filtered. The filtrate has saponification number=66.3, and12.9% unreacted polyisobutylene.

EXAMPLE 8-A

The procedure of Example 7-A is repeated except the reaction andstripping is conducted at 140° C. The product has saponificationnumber=91.3 and 15.4% unreacted polyisobutylene.

EXAMPLE 9-A

The procedure of Example 7-A is repeated except the reaction isconducted at 160° C. and stripping is to 145° C. at 30 mm Hg the producthas saponification number=55 and contains 8.6% unreactedpolyisobutylene.

EXAMPLE 10-A

A reactor is charged with 1067 parts of the polyisobutylene of Example7-A, 154 parts GMHA, 4 parts 70% aqueous methane sulfonic acid and 0.1part silicone antifoam. The materials are heated, under N₂, to 135° C.and are held at temperature for a total of 13 hours. An additional 154parts GMHA and 2 parts methane sulfonic acid are added and the reactionis continued at 135° C. for 7 more hours collecting distillate. Thematerials are stripped to 135° C. at 15 mm Hg for 3 hours and filteredat 135° C. The materials have saponification number=71 and 9.8%unreacted polyisobutylene.

EXAMPLE 11-A

A reactor is charged with 350 parts of the polyisobutylene of Example7-A, 50.4 parts GMHA, 2 parts 70% methane sulfonic acid, 8 parts waterand 0.1 part silicone antifoam. The materials are heated, under N₂, to135° C. and are held at temperature while collecting 20.9 partsdistillate. The materials are stripped to 135° C. at 15 mm Hg for 3hours then filtered. The filtrate has saponification number=50.5 and7.2% unreacted polyisobutylene.

EXAMPLE 12-A

A reactor is charged with 1350 parts polyisobutylene (Glissopal 2300,BASF) having M_(n) about 2300 and about 90% terminal vinylidine groups,66.1 parts GMHA and 3.5 parts 70% aqueous methane sulfonic acid. Thematerials heated, under N₂, to 135° C. and are held at temperature for 7hours while collecting distillate. The materials are stripped to 145° C.at 25 mm Hg for 0.5 hour then filtered. The filtrate has saponificationnumber=16.5 and 22.7% unreacted polyisobutylene.

EXAMPLE 13-A

A reactor is charged with 699 parts of the polyisobutylene of Example12-A, 38.1 parts GMHA, 2 parts 70% aqueous methane sulfonic acid and 0.1part silicone antifoam. The materials are heated, under N₂, to 135° C.and are held at temperature for a total of 9 hours while collectingdistillate. The materials are filtered. The filtrate has saponificationnumber=20 and 57% unreacted polyisobutylene.

EXAMPLE 14-A

The procedure of Example 12-A is repeated employing 1547 parts ofGlissopal 2300, 126.2 parts GMHA, and 4 parts methane sulfonic acid. Theproduct has saponification number=35 and 3.1% unreacted polyisobutylene.

EXAMPLE 15-A

A reactor is charged with 1000 parts of the polyisobutylene of Example12-A, 54.4 parts GMHA, 4 parts titanium isopropoxide and 0.1 partsilicone antifoam. The materials are heated, under N₂, to 125° C. andare held at temperature for 6 hours while collecting 20 partsdistillate. The materials are stripped to 125° C. at 15 mm Hg for 1 hourthen filtered. The filtrate has saponification number 7.3 and 78.95%unreacted polyisobutylene.

EXAMPLE 16-A

The procedure of Example 12-A is followed employing 2206 parts of thepolyisobutylene of Example 12-A, 240 parts GMHA, 3 parts methanesulfonic acid and 0.1 part silicone antifoam. The materials havesaponification number=42 and 1.8% unreacted polyisobutylene.

EXAMPLE 17-A

A reactor is charged with 3924 parts of the polyisobutylene of Example12-A, 320.2 parts GMHA, 12 parts methane sulfonic acid, and 0.2 partssilicone antifoam. The materials are heated, under N₂, to 135° C. andare held at temperature for 6 hours while collecting distillate. Thematerials are stripped to 135° C. at 20 mm Hg for 1 hour, the residue isdiluted with 2772 parts mineral oil diluent then filtered. The producthas saponification number=19.5 and has 7.2% unreacted polyisobutylene.

EXAMPLE 18-A

A reactor is charged with 55 parts of Trilene® 67, andethylene-propylene-ethylenenorbornene terpolymer having a viscosityaverage molecular weight of about 7500 and an iodine number of 19, and165.6 parts mineral oil. The materials are heated to 110° C. under N₂followed by addition of 3.3 parts GMHA and 0.21 parts 70% aqueousmethane sulfonic acid. The materials are heated to 145° C. and held attemperature for 6 hours followed by stripping at 145° C. and 12 mm Hgfor 1 hour.

EXAMPLE 19-A

A reactor is charged with 350 parts of a polyisobutene having M_(n) =940(VPO) and bromine number=17, 42 parts GMHA and 0.5 parts 70% aqueousmethane sulfonic acid. The materials are heated, under N2, to 135° C.and maintained at temperature for 6 hours while collecting 12.1 partsdistillate. The materials are filtered at 135° C. The product hassaponification number=50 and has 29.3% unreacted polyisobutene.

EXAMPLE 20-A

The procedure of Example 19-A is repeated employing 525 parts of apolyisobutene having M_(n) =1700 (VPO) and bromine number=6, 63 partsGMHA and 1.0 part methane sulfonic acid. The product has saponificationnumber=44 and contains 19.4% unreacted polyisobutene.

Also contemplated herein is a process which further comprises reactingthe product of the reaction of reactants (A) and (B) with (C) ammonia,hydrazine or an amine having at lest one condensable N--H group and/or(D) a reactive metal or a reactive metal compound. Products obtainedthereby are useful as performance improving additives for lubricatingoil compositions and for normally liquid fuels.

Suitable reactants (C) and (D) are described hereinbelow.

(C) Ammonia, Hydrazine and Amine Reactants

Suitable (C) reactants, as defined herein, include ammonia, hydrazines,monoamines or polyamines. The (C) reactants must contain at least onecondensable N--H group. The monoamines generally contain from 1 to about24 carbon atoms, preferably 1 to about 12, and more preferably 1 toabout 6. Examples of monoamines useful in the present invention includeprimary amines, for example methylamine, ethylamine, propylamine,butylamine, octylamine, and dodecylamine. Examples of secondary aminesinclude dimethylamine, diethylamine, dipropylamine, dibutylamine,methylbutylamine, ethylhexylamine, etc. Tertiary monoamines will notresult in formation of an amide, but can form salts with carboxylicacids.

In another embodiment, the monoamine may be a hydroxyamine. Typically,the hydroxyamines are primary or secondary alkanolamines or mixturesthereof. As stated above, tertiary monoamines will not react to formamides; however tertiary alkanol monoamines sometimes can react to forma tertiary amino group containing ester. Alkanol amines that can reactto form amide can be represented, for example, by the formulae:##STR11## wherein each R₄ is independently a hydrocarbyl group of one toabout 22 carbon atoms or hydroxyhydrocarbyl group of two to about 22carbon atoms, preferably one to about four, and R' is a divalenthydrocarbyl group of about two to about 18 carbon atoms, preferably twoto about four. The group --R'--OH in such formulae represents thehydroxyhydrocarbyl group. R' can be an acyclic, alicyclic or aromaticgroup. Typically, R' is an acyclic straight or branched alkylene groupsuch as an ethylene, 1,2-propylene, 1,2-butylene, 1,2-octadecylene, etc.group. When two R⁴ groups are present in the same molecule they can bejoined by a direct carbon-to-carbon bond or through a heteroatom (e.g.,oxygen, nitrogen or sulfur) to form a 5-, 6-, 7- or 8-membered ringstructure. Examples of such heterocyclic amines include N-(hydroxyllower alkyl)-morpholines, -thiomorpholines, -piperidines, -oxazolidines,-thiazolidines and the like. Typically, however, each R⁴ isindependently a methyl, ethyl, propyl, butyl, pentyl or hexyl group.

Examples of these alkanolamines include mono-, di-, and triethanolamine,diethylethanolamine, ethylethanolamine, butyldiethanolamine, etc.

The hydroxyamines can also be ether N-(hydroxyhydrocarbyl)amines. Theseare hydroxy poly(hydrocarbyloxy) analogs of the above-described hydroxyamines (these analogs also include hydroxyl-substituted oxyalkyleneanalogs). Such N-(hydroxyhydrocarbyl)amines can be convenientlyprepared, for example, by reaction of epoxides with aforedescribedamines and can be represented by the formulae: ##STR12## wherein x is anumber from about 2 to about 15 and R₄ and R' are as described above. R₄may also be a hydroxypoly (hydrocarbyloxy) group.

Other useful amines include ether amines of the general formula

    R.sub.6 OR.sub.1 NHR.sub.7

wherein R⁶ is a hydrocarbyl group, preferably an aliphatic group, morepreferably an alkyl group, containing from 1 to about 24 carbon atoms,R₁ is a divalent hydrocarbyl group, preferably an alkylene group,containing from two to about 18 carbon atoms, more preferably two toabout 4 carbon atoms and R₇ is H or hydrocarbyl, preferably H oraliphatic, more preferably H or alkyl, more preferably H. When R₇ is notH, then it preferably is alkyl containing from one to about 24 carbonatoms. Especially preferred ether amines are those available under thename SURFAM produced and marketed by Sea Land Chemical Co., Westlake,Ohio.

The amine may also be a polyamine. The polyamine may be aliphatic,cycloaliphatic, heterocyclic or aromatic. Examples of the polyaminesinclude alkylene polyamines, hydroxy containing polyamines,arylpolyamines, and heterocyclic polyamines.

Alkylene polyarnines are represented by the formula ##STR13## wherein nhas an average value between about 1 and about 10, preferably about 2 toabout 7, more preferably about 2 to about 5, and the "Alkylene" grouphas from 1 to about 10 carbon atoms, preferably about 2 to about 6, morepreferably about 2 to about 4. R₅ is independently hydrogen or analiphatic or hydroxy-substituted aliphatic group of up to about 30carbon atoms. Preferably R₅ is H or lower alkyl, most preferably, H.

Alkylene polyamines include methylene polyamines, ethylene polyamines,butylene polyamines, propylene polyamines, pentylene polyamines, etc.Higher homologs and related heterocyclic amines such as piperazines andN-amino alkyl-substituted piperazines are also included. Specificexamples of such polyamines are ethylene diamine, diethylene triamine,triethylene tetramine, tris-(2-aminoethyl)amine, propylene diamine,trimethylene diamine, tripropylene tetramine, tetraethylene pentamine,hexaethylene heptamine, pentaethylenehexamine, aminoethyl piperazine,dimethyl aminopropylamine, etc.

Higher homologs obtained by condensing two or more of the above-notedalkylene amines are similarly useful as are mixtures of two or more ofthe aforedescribed polyamines.

Ethylene polyamines, such as some of those mentioned above, arepreferred. They are described in detail under the heading EthyleneAmines in Kirk Othmer's "Encyclopedia of Chemical Technology", 2dEdition, Vol. 7, pages 22-37, Interscience Publishers, New York (1965).Such polyamines are most conveniently prepared by the reaction ofethylene dichloride with ammonia or by reaction of an ethylene iminewith a ring opening reagent such as water, ammonia, etc. These reactionsresult in the production of a complex mixture of polyalkylene polyaminesincluding cyclic condensation products such as the aforedescribedpiperazines. Ethylene polyamine mixtures are useful.

Other useful types of polyamine mixtures are those resulting fromstripping of the above-described polyamine mixtures to leave as residuewhat is often termed "polyamine bottoms". In general, alkylene polyaminebottoms can be characterized as having less than two, usually less than1% (by weight) material boiling below about 200° C. A typical sample ofsuch ethylene polyamine bottoms obtained from the Dow Chemical Companyof Freeport, Tex., designated "E-100" has a specific gravity at 15.6° C.of 1.0168, a percent nitrogen by weight of 33.15 and a viscosity at 40°C. of 121 centistokes. Gas chromatography analysis of such a samplecontains about 0.93% "Light Ends" (most probably diethylenetriamine),0.72% triethylenetetramine, 21.74% tetraethylene pentaamine and 76.61%pentaethylene hexamine and higher (by weight). These alkylene polyaminebottoms include cyclic condensation products such as piperazine andhigher analogs of diethylenetriamine, triethylenetetramine and the like.

Another useful polyamine is a condensation product obtained by reactionof at least one hydroxy compound with at least one polyamine reactantcontaining at least one primary or secondary amino group. The hydroxycompounds are preferably polyhydric alcohols and amines. Preferably thehydroxy compounds are polyhydric amines. Polyhydric amines include anyof the above-described monoamines reacted with an alkylene oxide (e.g.,ethylene oxide, propylene oxide, butylene oxide, etc.) having two toabout 20 carbon atoms, preferably two to about four. Examples ofpolyhydric amines include tri-(hydroxypropyl)amine,tris-(hydroxymethyl)amino methane, 2-amino-2-methyl-1,3-propanediol,N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, andN,N,N',N'-tetrakis(2-hydroxyethyl) ethylenediamine.

Polyamine reactants, which react with the polyhydric alcohol or amine toform the condensation products or condensed amines, are described above.Preferred polyamine reactants include triethylenetetramine (TETA),tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), andmixtures of polyamines such as the above-described "amine bottoms".

The condensation reaction of the polyamine reactant with the hydroxycompound is conducted at an elevated temperature, usually about 60° C.to about 265° C. in the presence of an acid catalyst.

The amine condensates and methods of making the same are described inSteckel (U.S. Pat. No. 5,053,152) which is incorporated by reference forits disclosure to the condensates and methods of making.

In another embodiment, the polyamines are hydroxy-containing polyamines.Hydroxy-containing polyamine analogs of hydroxy monoamines, particularlyalkoxylated alkylenepolyamines can also be used. Such polyamines can bemade by reacting the above-described alkylene amines with one or more ofthe above-described alkylene oxides. Similar alkylene oxide-alkanolaminereaction products can also be used such as the products made by reactingthe aforedescribed primary, secondary or tertiary alkanolamines withethylene, propylene or higher epoxides in a 1.1 to 1.2 molar ratio.Reactant ratios and temperatures for carrying out such reactions areknown to those skilled in the art.

Specific examples of alkoxylated alkylenepolyamines includeN-(2-hydroxyethyl)ethylenediamine,N,N-di-(2-hydroxyethyl)-ethylenediamine, 1-(2-hydroxyethyl)piperazine,mono-(hydroxypropyl)-substituted tetraethylenepentamine,N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higher homologs obtainedby condensation of the above illustrated hydroxy-containing polyaminesthrough amino groups or through hydroxy groups are likewise useful.Condensation through amino groups results in a higher amine accompaniedby removal of ammonia while condensation through the hydroxy groupsresults in products containing ether linkages accompanied by removal ofwater. Mixtures of two or more of any of the aforesaid polyamines arealso useful.

In another embodiment, the polyamine may be a heterocyclic polyamine.The heterocyclic polyamines include aziridines, azetidines, azolidines,tetra- and dihydropyridines, pyrroles, indoles, piperidines, imidazoles,di- and tetrahydroimidazoles, piperazines, isoindoles, purines,N-aminoalkylmorpholines, N-aminoalkylthiomorpholines,N-aminoalkylpiperazines, N,N'-bisaminoalkyl piperazines, azepines,azocines, azonines, azecines and tetra-, di- and perhydro derivatives ofeach of the above and mixtures of two or more of these heterocyclicamines. Preferred heterocyclic amines are the saturated 5- and6-membered heterocyclic amines containing only nitrogen, or nitrogenwith oxygen and/or sulfur in the hetero ring, especially thepiperidines, piperazines, thiomorpholines, morpholines, pyrrolidines,and the like. Piperidine, aminoalkylsubstituted piperidines, piperazine,aminoalkylsubstituted piperazines, morpholine, aminoalkylsubstitutedmorpholines, pyrrolidine, and aminoalkyl-substituted pyrrolidines, areespecially preferred. Usually the aminoalkyl substituents aresubstituted on a nitrogen atom forming part of the hetero ring. Specificexamples of such heterocyclic amines include N-aminopropylmorpholine,N-amino-ethylpiperazine, and N,N'-diaminoethyl-piperazine. Hydroxy alkylsubstituted heterocyclic polyamines are also useful. Examples includeN-hydroxyethylpiperazine and the like.

In another embodiment, the amine is a polyalkene-substituted amine.These polyalkene-substituted amines are well known to those skilled inthe art. They are disclosed in U.S. Pat. Nos. 3,275,554; 3,438,757;3,454,555; 3,565,804; 3,755,433; and 3,822,289. These patents are herebyincorporated by reference for their disclosure of polyalkene-substitutedamines and methods of making the same.

Typically, polyalkene-substituted amines are prepared by reactinghalogenated-, preferably chlorinated-, olefins and olefin polymers(polyalkenes) with amines (mono- or polyamines). The amines may be anyof the amines described above. Examples of these compounds includepoly(propylene)amine; N,N-dimethyl-N-poly(ethylene/propylene)amine,(50:50 mole ratio of monomers); polybutene amine;N,N-di(hydroxyethyl)-N-polybutene amine;N-(2-hydroxypropyl)-N-polybutene amine; N-polybutene-aniline;N-polybutene-morpholine; N-poly(butene)ethylenediamine;N-poly(propylene)trimethylenedianiine;N-poly(butene)diethylene-triamine;N',N'-poly(butene)tetraethylenepentamine;N,N-dimethyl-N'-poly-(propylene)-1,3-propylenediamine and the like.

The polyalkene substituted amine is characterized as containing from atleast about 8 carbon atoms, preferably at least about 30, morepreferably at least about 35 up to about 300 carbon atoms, preferably200, more preferably 100. In one embodiment, the polyalkene substitutedamine is characterized by an n (number average molecular weight) valueof at least about 500. Generally, the polyalkene substituted amine ischaracterized by an n value of about 500 to about 5000, preferably about800 to about 2500. In another embodiment n varies between about 500 toabout 1200 or 1300.

The polyalkenes from which the polyalkene substituted amines are derivedinclude homopolymers and interpolymers of polymerizable olefin monomersof 2 to about 16 carbon atoms; usually 2 to about 6, preferably 2 toabout 4, more preferably 4. The olefins may be monoolefins such asethylene, propylene, 1-butene, isobutene, and 1-octene; or apolyolefinic monomer, preferably diolefinic monomer, such 1,3-butadieneand isoprene. Preferably, the polymer is a homopolymer. An example of apreferred homopolymer is a polybutene, preferably a polybutene in whichabout 50% of the polymer is derived from isobutylene. The polyalkenesare prepared by conventional procedures.

Another useful reactant (C) is an acylated polyamine. These includereaction products of carboxylic acids with an excess of polyamine toform an acylated nitrogen compound such as an amide or imide that has atleast one condensable N--H group available for reaction with the productobtained from the reaction of (A) and (B).

To form this reactant, virtually any acylating agent may be used such asfatty acids, polyolefin substituted succinic acids and anhydrides, andthe like. Preferred are polyisobutylene succinic acids and anhydrideswherein the polyisobutylene substituent is derived from polyisobutylenehaving M_(n) ranging from about 500 to about 2500.

It is generally preferred to utilize sufficient amine reactant (C) toconvert substantially all of the intermediate arising from reaction of(A) with (B) to product; however, conversion of at least 50%, morepreferably 75% is often acceptable. Preferably, at least 90%, morepreferably 99-100% conversion is effected.

The reaction with the (C) reactant to prepare the products of thisinvention is conducted at temperatures ranging from about 25° C. toabout 230° C. When the amine is an alkanolamine, an alkylene polyamineor a thioalkanol amine, N-containing heterocyclic group containingproducts such as imidazoline, oxazoline, or thiazoline formation mayform. These are frequently obtained by first preparing an amide thencontinuing the reaction at elevated temperature to generate imidazoline,thiazoline or oxazoline by removal of water.

Imidazoline formation will not occur with every amine; the amine musthave the structural element:

    H.sub.2 NCRCR--NH--R.sup.f.

Similarly, oxazoline formation can take place when the amine is aβ-hydroxyethyl amine, e.g.,

    HO--CR.sup.f.sub.2 CR.sup.f.sub.2 --NH.sub.2

β-thiolamines can react to form thiazolines.

In the above formulae, each R^(f) is independently H, alkoxyalkyl,hydroxyalkyl, hydrocarbyl, aminohydrocarbyl or N-alkoxyalkyl- orhydroxyalkyl-substituted amino hydrocarbyl.

Thus, if imidazoline, thiazoline or oxazoline formation is not desired,they may be avoided by employing amine reactants that do not provide theopportunity for imidazoline, thiazoline or oxazoline formation, or, ifthe amine employed can lead to oxazoline, thiazoline or imidazoline, tominimize formation thereof by conducting the reaction at the lowesttemperature to prepare amide at an acceptable rate and in acceptableamounts, or to avoid prolonged heating of the amide-containing product,once it has formed. Infrared analysis during the reaction is aconvenient means for determining the nature and extent of the reaction.

The product formed from the reaction of (A) and (B) is then reacted, attemperatures ranging from about 25° C. to about 230° C., preferably fromabout 60° C. to about 150° C., more often from about 100° C. to about110° C. with (C) ammonia, a hydrazine or an amine characterized by thepresence within its structure of at least one N--H group. Reactant (C)is used in amounts ranging from about 0.5 equivalents up to about 2moles, per mole of (B).

Products obtained by post-treating the acylated nitrogen compounds ofthis invention are also useful. Reagents such as urea, thiourea, carbondisulfide, aldehydes, ketones, carboxylic acids, hydrocarbon substitutedsuccinic anhydrides, nitrites, epoxides, boron compounds, phosphoruscompounds and the like are useful post-treating agents.

The Reactive Metals and Metal Compounds

The reactive metals include but are not limited to alkali metals,alkaline earth metals, zinc, cadmium, lead, cobalt, nickel iron,manganese and copper. Preferred are the alkali and alkaline earthmetals. Especially preferred are sodium, potassium, calcium and lithium.

Examples of reactive metal compounds are sodium oxide, sodium hydroxide,sodium carbonate, sodium methylate, sodium phenoxide, correspondingpotassium and lithium compounds, calcium oxide, calcium hydroxide,calcium carbonate, calcium methylate, calcium chloride, calciumphenoxide, and corresponding barium and magnesium compounds, zinc oxide,zinc hydroxide, zinc carbonate, cadmium chloride, lead oxide, leadhydroxide, lead carbonate, nickel oxide, nickel hydroxide, nickelnitrate, cobalt oxide, ferrous carbonate, ferrous oxide, cupric acetate,cupric nitrate, etc.

The above metal compounds are merely illustrate of those useful in thisinvention; however, the invention is not considered as limited to such.Suitable metals and metal containing reactants are disclosed in manyU.S. patents including U.S. Pat. Nos. 3,306,908; 3,271,310; and U.S.Pat. No. Re. 26,433.

The reaction product resulting from the reaction of the condensationproduct and the reactive metal or metal compound will preferablycomprise a substantially neutral metal salt, which metal salt is acarboxylate and/or phenate. However, the salts may contain up to about50% unreacted lactone, carboxylic acid, or ester group of mixturesthereof.

It is also to be understood that the salts of Formula (I) may also beslightly basic, that is they may contain a small excess (up to about10-15% excess) of metal beyond that which is normally expected based onthe stoichiometry of the components. The excess metal is not used forthe purpose of preparing overbased metals but for insuring that thereaction leading to salt formation reaction is driven to completion.

The following examples are intended to illustrate several derivatives ofthis invention as well as means for preparing same. Unless indicatedotherwise all parts are parts by weight, filtrations are conductedemploying a diatomaceous earth filter aid, and analytical values are byactual analysis. The abbreviations GPC and VPO refer to gel permeationchromatography and vapor phase osmometry, respectively, both proceduresbeing used to determine molecular weight. Aromatic hydrocarbons arecommercial aromatic hydrocarbon solvents having a flash point of about43° C. It is to be understood that these examples are intended toillustrate several compositions and procedures of the invention and arenot intended to limit the scope of the invention.

EXAMPLE 1-B

A reactor is charged 225 parts of the product of Example 4-A, 4.6 partsof an ethylene polyamine mixture having an average compositionscorresponding to tetraethylenepentamine, and 153.1 parts mineral oildiluent. The materials are heated, under nitrogen, for 6 hours at 160°C. while collecting distillate in a Dean-Stark trap. The materials arefiltered at 140° C. The product has percent nitrogen=0.33.

EXAMPLE 2-B

The process of Example 1-B is repeated employing 500 parts of theproduct of Example 5-A, 28.2 parts of the polyamine and 352.1 partsmineral oil diluent. The product contains 1.03% nitrogen.

EXAMPLE 3-B

The process of Example 1-B is repeated employing 350 parts of theproduct of Example 7-A, 19.9 parts of the polyamine and 246.6 partsmineral oil diluent. The product contains 1.0% nitrogen.

EXAMPLE 4-B

The process of Example 1-B is repeated employing 350 parts of theproduct of Example 7-A, 27.4 parts of the polyamine and 251.6 partsmineral oil diluent. The product contains 1.3% nitrogen.

EXAMPLE 5-B

The process of Example 1-B is repeated employing 350 parts of theproduct of Example 7-A, 29.9 parts of the polyamine and 253.3 partsmineral oil diluent. The product contains 1.42% nitrogen.

EXAMPLE 6-B

The process of Example 1-B is repeated employing 230 parts of theproduct of Example 8-A, 24.7 parts of the polyamine and 169.8 partsmineral oil diluent. The product contains 2.01% nitrogen.

EXAMPLE 7-B

A reactor is charged with 600 parts of the products of Example 12-A,14.6 parts of a polyamine bottoms containing about 31.5% nitrogen(HPA-X, Union Carbide) and 410 parts mineral oil diluent. The materialsare heated for 6 hours, under N₂, at 160° C. and filtered. The filtratecontains 0.45% nitrogen.

EXAMPLE 8-B

The process of Example 7-B is repeated employing 300 parts of theproduct of Example 13-A, 12.3 parts of the polyamine bottoms and 208parts of mineral oil diluent. The product contains 0.72% nitrogen.

EXAMPLE 9-B

The process of Example 7-B is repeated employing 5100 parts of theproduct of Example 17-A, 132.6 parts of the polyamine bottoms and 88.4parts of mineral oil diluent. The reaction is conducted at 170° C. for 7hours and the filtration is done at 145° C. The product contains 0.81%nitrogen.

EXAMPLE 10-B

A reactor is charged with 300 parts of the product of Example 13-A, 10.8parts of the polyamine bottoms of Example 7-B, 8.9 parts of N-tallowpropanediamine (Duomeen T, Akzo) and 213 parts mineral oil diluent. Thematerials are heated to 180° C. and maintained at temperature for 6hours while collecting distillate. The materials are filtered at 150° C.The product contains 0.78% nitrogen.

EXAMPLE 11-B

A reactor is charged with 224 parts of the product of Example 18-A, 85parts of a 60% by weight in oil solution of the reaction product of apolyisobutene (M_(n) 1000) substituted succinic anhydride with thecondensation product of an ethylene polyamine bottoms withtris-hydroxymethylaminomethane. The materials are reacted, under N₂, at165° C. for 5 hours, followed by dilution in 165.6 parts mineral oil.The solution is filtered through cloth. The filtrate contains 0.377%nitrogen.

EXAMPLE 12-B

A reactor is charged with 500 parts of polyisobutylene (Ultravis 10), 72parts GMHA and 2 parts 70% aqueous methane sulfonic acid. The materialsare heated under N₂ to 160° C. and maintained at temperature for 6 hourswhile collecting distillate in a Dean-Stark trap. To this material areadded 41.9 parts N-aminoethylpiperazine over 0.1 hour followed byreaction at 160° C. for 5 hours while collecting distillate. Thematerials are diluted with 248.1 parts aromatic diluent and filtered.The filtrate contains 1.54% nitrogen.

EXAMPLE 13-B

A reactor is charged with 600 parts of the product of Example 2-A and 8parts Ca(OH)₂ followed by heating at 150° C. for 4 hours, dilution with200 part mineral oil and filtration

The Lubricating Oil Compositions

The Oil of Lubricating Viscosity

In one embodiment of this invention, the compositions are used asadditives in lubricating oil compositions. The lubricating compositionsemploy an oil of lubricating viscosity, including natural or syntheticlubricating oils and mixtures thereof. Mixtures of mineral oil andsynthetic oils, particularly polyalphaolefin oils and polyester oils,are often used. The lubricating composition of this invention comprise amajor amount of an oil of lubricating viscosity and a minor amount ofthe composition of this invention.

By major amount is meant greater than 50% by weight, while minor amountmeans less than 50% by weight, based on the total weight of thecomposition.

Natural oils include animal oils and vegetable oils (e.g. castor oil,lard oil and other vegetable acid esters) as well as mineral lubricatingoils such as liquid petroleum oils and solvent-treated or acid treatedmineral lubricating oils of the paraffinic, naphthenic or mixedparaffinic-naphthenic types. Hydrotreated or hydrocracked oils areincluded within the scope of useful oils of lubricating viscosity.

Oils of lubricating viscosity derived from coal or shale are alsouseful. Synthetic lubricating oils include hydrocarbon oils andhalosubstituted hydrocarbon oils such as polymerized andinterpolymerized olefins, etc. and mixtures thereof, alkylbenzenes,polyphenyl, (e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.),alkylated diphenyl ethers and alkylated diphenyl sulfides and theirderivatives, analogs and homologues thereof and the like.

Alkylene oxide polymers and interpolymers and derivatives thereof, andthose where terminal hydroxyl groups have been modified byesterification, etherification, etc., constitute other classes of knownsynthetic lubricating oils that can be used.

Another suitable class of synthetic lubricating oils that can be usedcomprises the esters of dicarboxylic acids and those made from C₅ to C₁₂monocarboxylic acids and polyols or polyol ethers.

Other synthetic lubricating oils include liquid esters ofphosphorus-containing acids, polymeric tetrahydrofurans and the like,silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, orpolyaryloxy-siloxane oils and silicate oils.

Hydrotreated naphthenic oils are well known.

Unrefined, refined and rerefined oils, either natural or synthetic (aswell as mixtures of two or more of any of these) of the type disclosedhereinabove can used in the compositions of the present invention.Unrefined oils are those obtained directly from a natural or syntheticsource without further purification treatment. Refined oils are similarto the unrefined oils except they have been further treated in one ormore purification steps to improve one or more properties. Rerefinedoils are obtained by processes similar to those used to obtain refinedoils applied to refined oils which have been already used in service.Such rerefined oils often are additionally processed by techniquesdirected to removal of spent additives and oil breakdown products.

Specific examples of the above-described oils of lubricating viscosityare given in Chamberlin III, U.S. Pat. No. 4,326,972 and European PatentPublication 107,282, both of which are hereby incorporated by referencefor relevant disclosures contained therein.

A basic, brief description of lubricant base oils appears in an articleby D. V. Brock, "Lubrication Engineering", Volume 43, pages 184-5,March, 1987, which article is expressly incorporated by reference forrelevant disclosures contained therein.

Other Additives

The lubricating oil compositions of this invention may contain minoramounts of other components. The use of such components is optional andthe presence thereof in the compositions of this invention will dependon the particular use and level of performance required. Thus thesecomponents may be included or excluded.

The compositions may comprise a zinc salt of a dithiophosphoric acid.Zinc salts of dithiophosphoric acids are often referred to as zincdithiophosphates, zinc O,O-dihydrocarbyl dithiophosphates, and othercommonly used names. They are sometimes referred to by the abbreviationZDP. One or more zinc salts of dithiophosphoric acids may be present ina minor amount to provide additional extreme pressure, anti-wear andanti-oxidancy performance.

In addition to zinc salts of dithiophosphoric acids discussedhereinabove, other additives that may optionally be used in thelubricating oils of this invention include, for example, detergents,dispersants, viscosity improvers, oxidation inhibiting agents, metalpassivating agents, pour point depressing agents, extreme pressureagents, anti-wear agents, color stabilizers and anti-foam agents. Theabove-mentioned dispersants and viscosity improvers are used in additionto the additives of this invention.

Auxiliary extreme pressure agents and corrosion and oxidation inhibitingagents which may be included in the compositions of the invention areexemplified by chlorinated aliphatic hydrocarbons, organic sulfides andpolysulfides, phosphorus esters including dihydrocarbon andtrihydrocarbon phosphites, molybdenum compounds, and the like.

Viscosity improvers (also sometimes referred to as viscosity indeximprovers) may be included in the compositions of this invention.Viscosity improvers are usually polymers, including polyisobutenes,polymethacrylic acid esters, diene polymers, polyalkyl styrenes,alkenylarene-conjugated diene copolymers and polyolefins.Multifunctional viscosity improvers, other than those of the presentinvention, which also have dispersant and/or antioxidancy properties areknown and may optionally be used in addition to the products of thisinvention. Such products are described in numerous publicationsincluding those mentioned in the Background of the Invention. Each ofthese publications is hereby expressly incorporated by reference.

Pour point depressants are a particularly useful type of additive oftenincluded in the lubricating oils described herein. See for example, page8 of `Lubricant Additives" by C. V. Smalheer and R. Kennedy Smith(Lezius-Hiles Company Publisher, Cleveland, Ohio, 1967). Pour pointdepressants useful for the purpose of this invention, techniques fortheir preparation and their use are described in U.S. Pat. Nos.2,387,501; 2,015,748; 2,655,479; 1,815,022; 2,191,498; 2,666,748;2,721,877; 2,721,878; and 3,250,715 which are expressly incorporated byreference for their relevant disclosures.

Anti-foam agents used to reduce or prevent the formation of stable foaminclude silicones or organic polymers. Examples of these and additionalanti-foam compositions are described in "Foam Control Agents", by HenryT. Kerner (Noyes Data Corporation, 1976), pages 125-162.

Detergents and dispersants may be of the ash-producing or ashless type.The ash-producing detergents are exemplified by oil soluble neutral andbasic salts of alkali or alkaline earth metals with sulfonic acids,carboxylic acids, phenols or organic phosphorus acids characterized byat least one direct carbon-to-phosphorus linkage.

The term "basic salt" is used to designate metal salts wherein the metalis present in stoichiometrically larger amounts than the organic acidradical. The amount of excess metal present is denoted by the metalratio (MR) which is defined as the percentage of metal relative to thestoichiometric amount divided by 100. A neutral salt has MR=1. One withthree times the stoichiometric amount has MR=3, etc. Basic salts andtechniques for preparing and using them are well known to those skilledin the art and need not be discussed in detail here.

Ashless detergents and dispersants are so-called despite the fact that,depending on its constitution, the detergent or dispersant may uponcombustion yield a nonvolatile residue such as boric oxide or phosphoruspentoxide; however, it does not ordinarily contain metal and thereforedoes not yield a metal-containing ash on combustion. Many types areknown in the art, and any of them are suitable for use in the lubricantsof this invention. The following are illustrative:

(1) Reaction products of carboxylic acids (or derivatives thereof)containing at least about 34 and preferably at least about 54 carbonatoms with nitrogen containing compounds such as amine, organic hydroxycompounds such as phenols and alcohols, and/or basic inorganicmaterials. Examples of these "carboxylic dispersants" are described inBritish Patent number 1,306,529 and in many U.S. patents including thefollowing:

    ______________________________________                                        3,163,603      3,381,022                                                                              3,542,680                                               3,184,474 3,399,141 3,567,637                                                 3,215,707 3,415,750 3,574,101                                                 3,219,666 3,433,744 3,576,743                                                 3,271,310 3,444,170 3,630,904                                                 3,272,746 3,448,048 3,632,510                                                 3,281,357 3,448,049 3,632,511                                                 3,306,908 3,451,933 3,697,428                                                 3,311,558 3,454,607 3,725,441                                                 3,316,177 3,467,668 4,194,886                                                 3,340,281 3,501,405 4,234,435                                                 3,341,542 3,522,179 4,491,527                                                 3,346,493 3,541,012 RE 26,433                                                 3,351,552 3,541,678                                                         ______________________________________                                    

(2) Reaction products of relatively high molecular weight aliphatic oralicyclic halides with amines, preferably polyalkylene polyamines. Thesemay be characterized as "amine dispersants" and examples thereof aredescribed for example, in the following U.S. patents:

    ______________________________________                                               3,275,554                                                                            3,454,555                                                         3,438,757 3,565,804                                                         ______________________________________                                    

(3) Reaction products of alkyl phenols in which the alkyl groupscontains at least about 30 carbon atoms with aldehydes (especiallyformaldehyde) and amines (especially polyalkylene polyamines), which maybe characterized as "Mannich dispersants". The materials described inthe following U.S. patents are illustrative:

    ______________________________________                                               3,413,347                                                                            3,725,480                                                         3,697,574 3,726,882                                                           3,725,277                                                                   ______________________________________                                    

(4) Products obtained by post-treating the carboxylic amine or Mannichdispersants with such reagents are urea, thiourea, carbon disulfide,aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinicanhydrides, nitriles, epoxides, boron compounds, phosphorus compounds orthe like. Exemplary materials of this kind are described in thefollowing U.S. patents:

    ______________________________________                                        3,036,003                                                                              3,282,955     3,493,520                                                                              3,639,242                                       3,087,936 3,312,619 3,502,677 3,649,229                                       3,200,107 3,366,569 3,513,093 3,649,659                                       3,216,936 3,367,943 3,533,945 3,658,836                                       3,254,025 3,373,111 3,539,633 3,697,574                                       3,256,185 3,403,102 3,573,010 3,702,757                                       3,278,550 3,442,808 3,579,450 3,703,536                                       3,280,234 3,455,831 3,591,598 3,704,308                                       3,281,428 3,455,832 3,600,372 3,708,522                                          4,234,435                                                                ______________________________________                                    

(5) Interpolymers of oil-solubilizing monomers such as decylmethacrylate, vinyl decyl ether and high molecular weight olefins withmonomers containing polar substituents, e.g., aminoalkyl acrylates ormethacrylates, acrylamides and poly-(oxyethylene)-substituted acrylates.These may be characterized as "polymeric dispersants" and examplesthereof are disclosed in the following U.S. patents:

    ______________________________________                                               3,329,658                                                                            3,666,730                                                         3,449,250 3,687,849                                                           3,519,565 3,702,300                                                         ______________________________________                                    

The above-noted patents are incorporated by reference herein for theirdisclosures of ashless dispersants.

The above-illustrated additives may each be present in lubricatingcompositions at a concentration of as little as 0.001% by weight usuallyranging from about 0.01% to about 20% by weight, more often from about1% to about 12% by weight.

The compositions of the present invention are present in a minoramounts, often amounts ranging from about 1% to about 20% by weight,more often from about 3% to about 10% by weight, even more often fromabout 5% to about 8% by weight.

Additive Concentrates

The various additives described herein can be added directly to thelubricating oil or fuel. Preferably, however, they are diluted with asubstantially inert, normally liquid organic diluent such as mineraloil, naphtha, benzene, toluene or xylene, to form an additiveconcentrate. These concentrates usually comprise about 0.1 to about 80%by weight, frequently from about 1% to about 80% by weight, more oftenfrom about 10% to about 80% by weight, of the compositions of thisinvention and may contain, in addition, one or more other additivesknown in the art or described hereinabove. The balance comprises thenormally liquid organic diluent. Concentrations such as 15%, 20%, 30% or50% or higher may be employed.

Additive concentrates are prepared by mixing together, often at elevatedtemperature, the desired components.

Additive concentrates used for preparing lubricating oil compositionsare illustrated by the following examples. The amounts shown areindicated as parts by weight or parts by volume. Unless indicatedotherwise, components are indicated as parts or percentages by weight ofchemical present on an oil or diluent free basis. When products ofExamples set forth hereinabove are used, the amounts listed are asprepared, including diluent, if any. The abbreviation MR refers to metalratio, the relative amount of metal in an overbased salt compared to theamount expected based on stoichiometry. For example, MR=2 means theoverbased material contains twice the amount of metal compared to the"normal" stoichiometric amount.

Additive concentrates are prepared by blending the components listed inthe following Tables. Mineral oil is used to bring the total to 100parts.

                                      TABLE 1                                     __________________________________________________________________________    ADDITIVE CONCENTRATES                                                                           Example (Parts by Weight)                                   Component         A  B   C  D   E  F                                          __________________________________________________________________________    Ca overbased (MR ˜ 1.1) S-coupled                                                         4.2                                                                              4.2 4.69                                                                             4.69                                                                              4.69                                                                             4.69                                         alkyl phenate                                                                 Di-(nonylphenol) amine 1.89 1.89 2.12 2.12 2.12 2.12                          Ca overbased (MR ˜ 2.8) alkyl benzene 9.95 9.95 11.17 11.17 11.17                                        11.17                                        sulfonate                                                                     Mg overbased (MR ˜ 14.7) alkyl benzene 2.18 2.18 2.44 2.44 2.44                                          2.44                                         sulfonate                                                                     Silicone antifoam 0.01 0.01 0.01 0.01 0.01 0.01                               Zinc salt of mixed isopropyl-2-ethylhexyl 8.79 8.79 9.87 9.87 9.87 9.87       dithiophosphate                                                               Product of Example 1-B 54.47                                                  Product of Example 2-B  54.47                                                 Product of Example 3-B   48.90                                                Product of Example 4-B    48.90                                               Product of Example 5-B     48.90                                              Product of Example 6-B      48.90                                           __________________________________________________________________________

The lubricating compositions of this invention are illustrated in thefollowing Examples. The lubricating compositions are prepared bycombining the specified ingredients, individually or from concentrates,in the indicated amounts and oil of lubricating viscosity to make thetotal 100 parts by weight. The amounts shown are indicated as parts byweight. Unless indicated otherwise, where components are indicated asparts by weight, they are amounts of chemical present on an oil ordiluent free basis. Thus, for example, an additive comprising 50% oilused at 10% by weight in a blend, provides 5% by weight of chemical.Totals are 100% by weight or 100 parts by weight. However, whenreferring to incorporation of products of Examples set forth herein,amounts are as prepared, including any diluent.

EXAMPLES I-VI

Lubricating oil compositions are prepared by mixing together in amineral oil of lubricating viscosity (Exxon 15W-40), 7.5 parts of a 91%oil solution of an ethylene-propylene-diene copolymer, 0.08% of astyrene-maleate copolymer neutralized with aminopropyl morpholine, andthe indicated amount of the additive concentrates set forth in thefollowing table:

    ______________________________________                                        Additive Concentrate/Parts by Weight                                                  Example                                                               ______________________________________                                        I            Example A/13.31                                                    II Example B/13.31                                                            III Example C/11.86                                                           IV Example D/11.86                                                            V Example E/11.86                                                             VI Example F/11.86                                                          ______________________________________                                    

The Fuel Compositions

The Normally Liquid Fuels

As indicated hereinabove, the products of this invention may also beused as additives for normally liquid fuels.

Fuel compositions of this invention comprise a major amount of anormally liquid fuel, i.e., one which is liquid under normal conditionsof use, typically, at ambient temperature, and minor amounts of thecompositions of this invention, where major amount and minor amount areas defined hereinabove.

The fuels used in the fuel compositions of this invention are well knownto those skilled in the art and usually contain a major portion of anormally liquid fuel such as hydrocarbonaceous petroleum distillate fuel(e.g., motor gasoline as defined by ASTM Specifications D-439-89 andD-4814-91 and diesel fuel or fuel oil as defined in ASTM SpecificationsD-396-90 and D-975-91). Fuels containing non-hydrocarbonaceous materialssuch a alcohols, ether, organo-nitro compounds and the like (e.g.,methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane) arealso within the scope of this invention as are liquid fuels derived fromvegetable or mineral sources. Vegetable or mineral sources include, forexample, crude petroleum oil, coal, corn, shale, oilseeds and othersources.

Oxygenates are compounds covering a range of alcohol and ether type basefuel. They have also been used as the sole fuel component, but moreoften as a supplemental fuel used together with, for example, gasolineto form the well-known "gasohol" blend fuels. Oxygenate-containing fuelsare described in ASTM D-4814-91.

Methanol and ethanol are commonly used oxygenates. They are primarilyused as fuels. Other oxygenates, such as ethers, for examplemethyl-t-butyl ether, are more often used as octane number enhancers forgasoline.

Mixtures of fuels are useful. Examples of fuel mixtures are combinationsof gasoline and ethanol, diesel fuel and ether, gasoline andnitromethane, etc.

Particularly preferred fuels are gasoline, that is, a mixture ofhydrocarbons having an ASTM boiling point of 60° C. at the 10%distillation point to about 205° C. at the 90% distillation point,oxygenates, and gasoline-oxygenate blends, all as defined in theaforementioned ASTM Specifications for automotive gasolines. Mostpreferred is gasoline.

The fuel compositions of the present invention may contain otheradditives which are well known to those of skill in the art. These caninclude anti-knock agents such as tetra-alkyl lead compounds, leadscavengers such as halo-akanes, dyes, antioxidants such as hinderedphenols, rust inhibitors such as alkylated succinic acids and anhydridesand derivatives thereof, bacteriostatic agents, auxiliary dispersantsand detergents, gum inhibitors, fluidizers, metal deactivators,demulsifiers, anti-icing agents and the like. The fuel compositions ofthis invention may be lead-containing or lead-free fuels. Preferred arelead-free fuels.

The products of this invention provide a number of benefits to a treatedfuel, including detergency, anticorrosion and the like.

In one particular embodiment of this invention, the motor fuelcompositions contain an amount of additives sufficient to provide totalintake system cleanliness. In another embodiment, they are used inamounts sufficient to prevent or reduce the formation of intake valvedeposits or to remove them where they have formed.

As mentioned hereinabove, fluidizers may be used in the fuelcompositions of the instant invention. Useful fluidizers include naturaloils or synthetic oils, or mixtures thereof. Natural oils includemineral oils, vegetable oils, animal oils, and oils derived from coal orshale. Synthetic oils include hydrocarbon oils such as alkylatedaromatic oils, olefin oligomers, esters, including esters ofpolycarboxylic acids, polyols, polyethers, poly(oxyalkylene)glycols,alkylphenol-derived polyethers, and others.

Fluidizers are usually fuel soluble, meaning they are soluble in thefuel in amounts of at least 0.1% by weight, more preferably at least 1%by weight. Certain fluidizers, for example, butylene- and propyleneoxide derived fluidizers, are generally soluble in fuels at all levels.These are readily prepared from alcohol, glycol and phenol initiatorsunder superatmospheric conditions, preferably in the presence of basiccatalysts.

Especially preferred mineral oils are paraffinic oils containing no morethan about 20% unsaturation, that is, no more than 20% of the carbon tocarbon bonds are olefinic.

Specific examples of synthetic oil fluidizers are polyoxyalkylene mono-and polyols, ether derivatives thereof and N-vinylpyrrolidinone additionproducts thereof, polyalphaolefins, and hydrogenated polyalphaolefins.

Particularly useful synthetic oils are the polyether oils such as thosemarketed under the UCON tradename by Union Carbide Corporation,poly(oxyalkylene)glycols such as those marketed under the EMKAROXtradename by ICI Chemicals and described in EP 0647700-A1 based on U.S.Ser. No. 133442 filed Oct. 6, 1993 and polyester oils derived from apolyol and one or more monocarboxylic acids such as those marketed byHatco Corporation.

Other examples are polyoxyalkylene compounds prepared from C₁₋₃₀alcohols or C₇₋₂₄ alkylphenols and sufficient propylene- or butyleneoxide such that molecular weight ranges from about 200 to about 5,000,and monoethers and N-vinylpyrrolidinone addition products thereof.Additional fluidizers include polyoxyalkylene compounds prepared fromglycols or polyols having from 2 to about 10 carbon atoms and sufficientpropylene- or butylene oxide such that overall molecular weight rangesfrom about 200 to about 6,000 and ether derivatives thereof.

Preferably, the fluidizers have a kinematic viscosity ranging from about2 to about 25 centistokes at 100° C., preferably from about 4 to about20 centistokes, and often up to about 15 centistokes. If the viscosityof the fluidizer is too high, a problem that may arise is thedevelopment of octane requirement increase (ORI) wherein the octanevalue demands of the engine tend to increase with time of operation.

While both mineral oils and synthetic oils are generally useful asfluidizers over the entire preferred viscosity range, it has beenobserved that at the lower end of the viscosity range, synthetic oilstend to provide somewhat superior performance compared to mineral oils.

It has been found that fluidizers, particularly when used within theranges specified herein, together with the compositions of thisinvention, improve detergency and emissions, and reduce the tendencytoward valve sticking. Amounts of the various additives, includingindividual amounts to be used in the fuel composition, and relativeamounts of additives are given hereinafter.

The fuel compositions of this invention may contain auxiliarydispersants. A wide variety of dispersants are known in the art and maybe used together with the amide compounds described herein. Preferredauxiliary dispersants are Mannich type dispersants, acylatednitrogen-containing dispersants, aminophenol dispersants, aminocarbamatedispersants, ester dispersants and amine dispersants.

Acylated nitrogen-containing compounds include reaction products ofhydrocarbyl-substituted carboxylic acylating agents such as substitutedcarboxylic acids or derivatives thereof with ammonia or amines.Especially preferred are succinimide dispersants.

Acylated nitrogen-containing compounds are known in the art and aredisclosed in, for example, U.S. Pat. Nos. 4,234,435; 3,215,707;3,219,666; 3,231,587 and 3,172,892, which are hereby incorporated byreference for their disclosures of the compounds and the methods ofpreparation.

The auxiliary dispersant may also be an ester. These compounds areprepared by reacting a hydrocarbyl-substituted carboxylic acylatingagent with at least one organic hydroxy compound. In another embodiment,the ester dispersant is prepared by reacting the acylating agent with ahydroxyarnine. Preferred are succinic esters.

Carboxylic esters and methods of making the same are known in the artand are disclosed in U.S. Pat. Nos. 3,219,666, 3,381,022, 3,522,179 and4,234,435 which are hereby incorporated by reference for theirdisclosures of the preparation of carboxylic ester dispersants.

The carboxylic esters may be further reacted with at least one amine andpreferably at least one polyamine. These nitrogen-containing carboxylicester dispersant compositions are known in the art, and the preparationof a number of these derivatives is described in, for example, U.S. Pat.Nos. 3,957,854 and 4,234,435 which have been incorporated by referencepreviously.

Also included among the auxiliary dispersants are Mannich typedispersants. Mannich products are formed by the reaction of at least onealdehyde, at least one amine having at least one N--H group and at leastone hydroxyaromatic compound.

Mannich products are described in the following patents: U.S. Pat. No.3,980,569; U.S. Pat. No. 3,877,899; and U.S. Pat. No. 4,454,059 (hereinincorporated by reference for their disclosure to Mannich products).

The auxiliary dispersant may be a polyalkene-substituted amine.Polyalkene-substituted amines are well known to those skilled in theart. Typically, polyalkene-substituted amines are prepared by reactingolefins and olefin polymers (polyalkenes) and halogenated derivativesthereof with amines (mono- or polyamines). These amines are disclosed inU.S. Pat. Nos. 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,755,433;and 3,822,289. These patents are hereby incorporated by reference fortheir disclosure of hydrocarbyl amines and methods of making the same.

Aminophenols are also included among useful auxiliary dispersants thatmay be used in the fuel composition of this invention. Typically, suchmaterials are prepared by reducing hydrocarbyl substituted nitrophenolsto the corresponding aminophenol. Useful aminophenols include thosedescribed in Lange, U.S. Pat. Nos. 4,320,000 and 4,320,021. Aminophenolsand methods for preparing are described in U.S. Pat. Nos. 4,100,082 and4,200,545 to Clason et al, U.S. Pat. No. 4,379,065 (Lange) and U.S. Pat.No. 4,425,138 (Davis). It should be noted that the term "phenol" used inthe context of aminophenols is not intended to limit the compoundsreferred to in that manner as being only hydroxybenzene derivatives. Theterm "phenol" is intended to encompass hydroxy aromatic compounds,including hydroxybenzene compounds, naphthols, catechols and others asdescribed in the foregoing patents, all of which are incorporated hereinby reference for relevant disclosures contained therein.

Also included among useful auxiliary dispersants are aminocarbamatedispersants such as those described in U.S. Pat. No. 4,288,612, which isincorporated herein by reference for relevant disclosures containedtherein.

Treating levels of the additives used in this invention are oftendescribed in terms of pounds of additive per thousand barrels (PTB) offuel. PTB values may be converted to approximate values expressed asparts (by weight) per million parts (by weight) of fuel by multiplyingPTB by 4 for gasoline and by 3.3 for diesel oil and fuel oil. Todetermine precise values it is necessary that the specific gravity ofthe fuel is known. The skilled person can readily perform the necessarymathematical calculations.

The fuel compositions of this invention contain from about 5 to about500 pounds per thousand barrels (PTB) of fuel additive, preferably fromabout 10 to about 250 PTB, more preferably from about 20 to about 100PTB.

Fluidizers, when used, are generally present in amounts ranging fromabout 1 to about 500 PTB, more often from about 10 to about 250 PTB andmost preferably from about 10 to about 150 PTB.

Relative amounts by weight, of the nitrogen-containing compound tofluidizer oil typically range from about 1:0 that is, essentially freeof fluidizer, up to 1:10, more often from about 1:0.5-2:0, preferablyfrom about 1:0.75-1.25.

Additive Concentrates

As mentioned hereinabove, the additives for use in fuels may be suppliedas additive concentrates which are then diluted with normally liquidfuels.

The following Table illustrates additive concentrates for use in fuels.

    ______________________________________                                                       Concentrate (% by Weight)                                      Component        F-I       F-II                                               ______________________________________                                        Alkylated aromatic                                                                             15.76     19.2                                                 hydrocarbon.sup.1                                                             Product of Example 12-B 34 38                                                 Demulsifiers 0.22                                                             Polyether Oil.sup.2  42.8                                                     Mineral oil 45.94                                                             2-Ethylhexanol 4.54                                                         ______________________________________                                         .sup.1 = HISOL10, Ashland Chemical Co.                                        .sup.2 = EMKAROX AF20, ICI                                               

The following examples illustrate several fuel compositions of thisinvention. When referring to compounds described in the Examples,amounts are given in parts and percentages by weight as prepared. Unlessindicated otherwise, all other parts and percentages are by weight andamounts of additives are expressed in amounts substantially free ofmineral oil or hydrocarbon solvent diluent. The abbreviation `PTB` meanspounds of additive per thousand barrels of fuel.

The following Table illustrates several fuel compositions of the instantinvention comprising unleaded gasoline and the indicated amounts ofadditive in percent by weight concentrate in fuel.

    ______________________________________                                        UNLEADED GASOLINE + % WEIGHT ADDITIVE CONCENTRATE                                   Concentrate    F-A    F-B                                               ______________________________________                                        F-I              0.08                                                           F-II  0.07                                                                  ______________________________________                                    

While the invention has been explained in relation to its preferredembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thespecification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications that fallwithin the scope of the appended claims.

What is claimed is:
 1. A process comprising reacting, optionally in thepresence of an acidic catalyst selected from the group consisting oforganic sulfonic acids, heteropolyacids, Lewis acids, and mineralacids,(A) at least one olefinic compound containing at least one groupof the formula: ##STR14## and (B) at least one carboxylic reactantselected from the group consisting of compounds of the formula ##STR15##wherein R³ is H or an aliphatic group, R⁵ and R⁹ are independently loweralkyl;R⁴ is a divalent hydrocarbylene group, and n is 0 or 1, in amountsranging from 0.6 moles (B) per mole of (A) to 3 moles (B) per equivalentof (A).
 2. The process of claim 1 wherein the product formed fromreaction of (A) and (B) is further reacted with from about 0.5equivalents up to about 2 moles, per mole of (B) of at least one of(C)ammonia or a hydrazine or an amine characterized by the presence withinits structure of at least one H--N group.
 3. The process of claim 1wherein the product formed from reaction of (A) and (B) is furtherreacted with from about 0.5 equivalents up to about 2 moles of (B) of atleast one reactive metal or reactive metal compound.
 4. The process ofclaim 1 wherein the at least one reactant (B) is at least one compoundof the formula ##STR16## wherein R³ is H and R⁵ and R⁹ are lower alkylgroups selected from the group consisting of methyl, ethyl, propyl andbutyl and n=0, and the olefinic compound (A) has the general formula

    (R.sup.1)(R.sup.2)C═C(R.sup.6)(CH(R.sup.7)(R.sup.8))   (III)

wherein each of R¹ and R² is, independently, hydrogen or a hydrocarbonbased group and each of R⁶, R⁷ and R⁸ is, independently, hydrogen or ahydrocarbon based group.
 5. The process of claim 4 wherein each of R¹and R² is hydrogen and R⁶ is H or a lower alkyl group and the group(CH(R⁷)(R⁸)) is a hydrocarbyl group containing from 7 to about 5000carbon atoms.
 6. The process of claim 5 wherein the group (CH(R⁷)(R⁸))is an aliphatic group containing from about 30 to about 200 carbon atomsand the olefinic compound is derived from homopolymerized andinterpolymerized C₂₋₁₈ olefins, wherein the olefinic compound has M_(n)ranging from about 200 to about 7,000.
 7. The process of claim 4 whereinthe olefinic compound is a polyolefin comprising a mixture of isomers,at least about 50% by weight of the mixture comprising isomers of theformula

    H.sub.2 C═C(R.sup.6)(CH(R.sup.7)(R.sup.8))

wherein R⁶ is H or lower alkyl.
 8. The process of claim 6 wherein thepolyolefin is a polybutene and R⁶ is methyl.
 9. The process of claim 4wherein the olefinic compound is a polyolefin comprising a mixture ofisomers wherein from about 50% to 65% are trisubstituted olefins whereinone substituent contains from 2 to about 5000 carbon atoms and the othertwo substituents are lower alkyl.
 10. The process of claim 1 wherein theolefinic compound is selected from the group consisting of a linearα-olefin containing from 8 to about 28 carbon atoms, anethylene-alpha-olefin copolymer, and an ethylene-alpha olefin-dieneterpolymer.
 11. The process of claim 2 wherein (C) is selected from thegroup consisting of an alkylene polyamine, an alkylene polyamine bottomsproduct, and a condensed polyamine derived from at least onehydroxy-containing material and at least one alkylene polyamine oralkylene polyamine bottoms product.
 12. A composition prepared by theprocess of claim
 1. 13. A composition prepared by the process of claim2.
 14. An additive concentrate for formulating lubricating oil or fuelcompositions comprising from about 20% to about 99% by weight of anormally liquid, substantially inert organic diluent and from about 10%to about 80% by weight of the composition described in claim
 13. 15. Alubricating composition comprising a major amount of an oil oflubricating viscosity and a minor amount of the composition described inclaim 13.